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Flash photolysis study for reactions of NO 3 · with sulfur compounds in acetonitrile solution
Author(s) -
Akiho Seiji,
Ito Osamu,
Iino Masashi
Publication year - 1989
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550210806
Subject(s) - chemistry , reaction rate constant , dimethyl sulfide , flash photolysis , acetonitrile , photochemistry , sulfone , sulfide , sulfur , electron transfer , dimethyl sulfoxide , kinetic isotope effect , deuterium , reaction rate , organic chemistry , kinetics , catalysis , physics , quantum mechanics
The rate constants for the reaction of NO 3 · with sulfur compounds in acetonitrile have been determined by the flash photolysis method. The rate constant for dimethyl sulfone (2.7 × 10 4 M −1 s −1 at −10°C) is larger than that of the deuterium derivative, indicating that NO 3 · abstracts the hydrogen atom from dimethyl sulfone. In the case of dimethyl sulfide, the rate constant was evaluated to be 1.5 × 10 9 M −1 s −1 at −10°C; the transient absorption band attributable to the cation radical was observed after the decay of NO 3 ·, suggesting the electron transfer reaction from the sulfide to NO 3 ·. For diphenyl sulfide and dimethyl disulfide, the electron transfer reactions were also confirmed. For dimethyl sulfoxide, the reaction rate constant of 1.2 × 10 9 M −1 s −1 (at −10°C) was not practically affected by the deuterium substitution, suggesting that NO 3 · adds to sulfur atom forming (CH 3 ) 2 Ṡ(O)‐ONO 2 . On the other hand, for diphenyl sulfoxide, the electron transfer reaction occurs. By the comparison of these rate constants in acetonitrile solution with the reported rate constants in the gas phase, the change of the reaction paths was revealed.